Reaction product of a polyalkylene polysulfide and a polyfunctional aziridine ring-containing compound



United States Patent 3,119,782 REACTION PRODUCT OF A POLYALKYLENE POLYSULFIDE AND A POLYFUNCHONAL AZLRIDINE RING-CONTAINING COMPOUND Paul Frans, Lincoln Township, Washington County, Minn asslgnor to Minnesota Mining and Manufacturing Company, St. Paul, Minn, a corporation of Delaware No Drawing. Filed Nov. 1 1960, Ser. No. 66,402 20 Claims. (C 260-42) This invention relates to polymeric compositions and more particularly to copolymers of polyalkylene polysulfide prepolymers with certain polyfunctional aziridine rings containing monomers.

This applimtion is continuation-in-part of my prior copcnding application Serial Number 709,471, filed January 17, 1958, now abandoned.

Heretoforc, in order to form room temperature-curing polysulfide rubber systems, it has been the practice to mix a polyalkylene polysulfide prepolymcr with metallic oxide accelerator such as of lead dioxide, zinc oxide or the like. Although such systems are widely used, they have several inherent disadvantages. Thus, for example, because the lead dioxide catalyst is a solid having a specific gravity more than seven times that of the polyalkylenc polysulfide prepolymers, it has been difiicult in many applications to get sufficient mixing between the prepolymer and the accelerator to avoid unevenness in speed and quality of cure and consequently of the resulting rubber. in addition, the resulting cured rubbers have been dark colored and opaque, which is a disadvantage in the production of white or light-colored objects. Other conventional curing agents for polyalltylenc polysuliide prepolymers are more easily blended into the said prepolymers (e.g. p-quinondioxime and diphenylguanidine), but such systems require an extended heat cycle to cure and are thus not useful in applications in which room temperature curing is required. Furthermore, only negligible adhesion is developed to common materials of construction, such as metals and glass, when either of the above-described curing systems is used. Consequently, it has been necessary to alter the basic properties of these systems to improve their adhesive characteristics by relatively expensive and difficult techniques of compounding and to improve their adhesion by developing primers for specific surfaces.

It is an object of the present invention to produce dense, tough, often transparent or translucent and lightcolored resinous or elastomeric solid copolymers of polyalkylene polysulfide prepolymers with certain polyfunctional aziridine ring containing monomers, which copolymers adhere strongly to common materials of construction such as glass and metals without primers and which cure at relatively low temperatures. Another ob ject of the invention is to provide relatively stable liquid mixtures of polyalkylene polysulfide prepolymers with certain polyfunotional aziridine ring-containing monomers (also sometimes referred to herein as polyfunctionai alkylenimine derivatives) which blend easily and uniformly with liquid curing agents and cure smoothly at low temperatures to produce elastomers having superior heat stability and solvent resistance together with good resistance to high humidity. Still another object of the invention is to provide rubber-like polymers having improved color, compatibility and working propertlm. Further objects of the invention will be apparent from the disclosure hereinafter made.

In accordance with the above and other objects of the invention it has been found that when polyalk-ylene polysulfide prepolymers are copolymerized with polyfunctional alkyienimine derivatives, resinous or elastomeric 3,119,782 Patented Jan. 28, 1964 ice compositions are produced which have highly advantageous properties.

The compositions of the invention have a high degree of heat stability while retaining desirable mechanical and chemical properties at high temperature. They have excellent solvent resistance as well as resistance to water and high humidity and, in addition, adhere readily to a wide-variety of surfaces such as glass and metals when eopolymerized in contact with said surfaces. They are often colorless and transparent or of such a light color that they can be used in the production of white or lightcolored resinous or elastomerie products. They can be mixed and compounded in simple, open mixing equipment rather than closed containers and ball mills; and they may be cast in inexpensive open molds, rather than high pressure and/or high temperature molds. When thus cast, they can be cured at surprisingly low temperatures, often at room temperature and when so cured, they are remarkably free from gas formation; yet they have useful pot lives in spite of their low temperature curing properties. The systems are characterized funther .by ordinarily requiring no solvents, so that they can be prepared as mixtures containing solid-forming components. The low temperature curing properties of the compositions of the invention enlarge their area of utility greatly, e.g. in applications (as in encapsulation) in which parts to be covered with resin are so fragile or of such materials that they are destroyed by heat, and in applications in which it is diliicult or undesirable to heat the resin and parts to be coated until suiliciently intimate contact between resin and parts is obtained. The solvcntlcss liquid systems of the invention cure with substantially no volusne change to yield solids which closely conform to the mold or container, and are easily bonded to metals and glass. Thus the compositions have utility as sealants and may be used to seal solvent storage tanks and to weather-proof joints between metal and glass parts in building construction.

Regarding the term "polyalkylene polysuliide prepolymers" as used herein, reference is made to those polymers described, for example, in US. Patents No. 1,890,191, 2,049,974, 2,l00,35l, 2,216,044, 2,466,963, 2,474,859, and 2,9l0,922 and in a publication by J orczak et al. of Thiokol Corporation, Trenton, New Jersey, in an article published in industrial and Engineering Chemistry, vol. 43, page 324, February i, which illustrate the type of prepolymcr useful for the purposes of the invention. The various polyalkylene polysulfide prepolymers useful in the present invention are polyfunctional in terms of meroaptan groups and contain recurring disulfidc linkages (-SS-). they are produced in the form of liquids, solids and dispersions and are sometimes referred to as polyfunetionalliquid mercaptans" (when in liquid form). Difunctionai polyalkylene polysulfide prepolymers which can be used in preparing the compositions of the present invention are those having the formula:

where z is an integer from 3 to 100 or more and R is a radical of the type disclosed in the said publication by Iorczak et al. Usually the radical R' can be represented by the formula:

iolyalkylene polysulfide prepolymers having the abovementioned formula are available with varying functionality and all are suitable in the preparation of the compounds of the present invention.

Although the invention can be used with any of the polyalkylene polysultide prepolymers, whether in liquid or solid form, particular attention will drawn, for purposes of illustration, to' the uses of the invention with the Their molecular weights may vary from about 200 to about 30,000 or higher. Normally liquid polymers are preferred for use in the present invention, such liquid polymers having an average molecular weight of from about 500 to 20,000 or higher, as determined in the familiar manner by means of end group titration. Liquid polymers in this range are viscous liquids at ordinary temperatures, have the consistency of thin syrup or molasses, and a viscosity of between about 3 and 1,500 poises. The degree of copolymerization employed in the manufacture of the polyalkylene polysulfide prepolymer and the average molecular weight thereof influences the physical properties. Generally, the use of a liquid polyalkylene polysullide prepolymer having a lower average molecular weight (say below 3 000) tends to produce harder bodies than a liquid polymer having a higher average molecular weight, the latter tending to produce bodies having a lower Shore hardness but better tear resistance. These tendencies are of course particularly strong in eopolymers of the invention in which a relatively large amount of the oiyalkylene polysultide prepolymer is used with respect to the polyfunctional ethylenimine.

The polyfunetional alkylenimine derivatives which are employed in this invention are alkylenirnine derivatives of the formula:

s 1 it'R" where Q is an n vaient radical, n is 2 or more (preferably 2 or 3), N is linked to an atom having a valence of 4 or 5, and R and R" are hydrogen or an alkyl group containing not more than 8 carbon atoms and preferably containing from i to 4 carbon atoms. Q may be an nliphatic, aromatic or alicycllc organic radical which does not contain an active hydrogen but which may contain atoms other than carbon, such as oxygen, sulfur, etc. This includes, for example, compounds in which Q is -SO,R""SO;-, wherein R"" is a divalent organic linking group which contains no active hydrogen, preferably 55 a divalent aliphatic, aromatic or alicyclic radical (such as N.N'-bis-2-methyledrylene-l,3-benzene disulfonamide; N.N' bis 1,2 ethylene 1,3 butanedisulfonamide; N.N bis 1,2 ethylene 1,4 butanedisulfonamlde and N,N' bis 1,2 ethylene 1,3 propanedisulfonamide) and compounds in which Q is a trivalent organic radical (such as N,N', "-trisethylenetrimesamide; N,N',N"-tris- 2 methylethylenetrimesarnide; N,N,'N" tris 2 butylfiur, etc., but does not contain any active hydrogen atoms, i.e. hydrogen which isactive to the Zercwitinoiftest (inert to Grignard reagents).

In still another group of alkylenimine derivatives which are employed'in this invention, Q may contain a i=0 or i=S l l radical, such as these compounds in which Q is B'-i|'-O wherein R is a monovalent or divalent organic linking group (preferably aliphatic, aromatic or alicyclic) which may contain atoms other than carbon, e.g. oxygen, sulfur, etc., but does not contain any active hydrogen atoms, i.e. hydrogen which is active to the Zerewitinoff test (inert to Grignard reagents).

The phosphoruscontnining alkylenirnine derivatives include for example, N,N',N"-tris-ethylencphosphoric triamide; N,N,N" tris ethylenethiophosphoramide; N,N- diethyl N',N" diethylenethiophos'phoramide; N,N' diethylenebenzene thiophosphorodiamide; N (3 oxa-pentamethylene)-N',N"-diethylcne phosphoric tria-mide; 'N,N'-

diethylene benzene phosphondiamide; N,N-diethylene ethane phosphondiamide; butyl N,N'-diethy-lenephosphorodinmidate; butyl N,N' di 2 methylethylenephosphorodiamidate; hexyl-N,N' diethylene phosphorodiamide; N,N' dioctyl N',N" diethylenephosphoric triamide; N,N',N" tris(l,l dimethylethylene) phosphoric triamide; N,N' dibutyl N'.N" diethyiene phosphoric triamide; parachlorophenyl N,N' di 2 methylethylene phosphoric diamide; etc.

The earboxyi containing curing agents which are particuiarly preferred have the formula:

Us O O Oils 1 NtnaFMna/ I nIRII described in us. Serial No. 850,54l, filed November 3,

1959. Generally, their preparation involves the reaction of a 1,2-alkylenimine in a water phase with a solution of a ehloroearbonate of a difunctional alcohol in a water inrniscible organic solvent, in the presence of an acid acceptor, ata temperature between about -5' C. and 30' C.; The following Example A illustrates the preparation.

EXAMPLE A A 250 mi. three necked flask was equipped with a" ethylenetrimesamidc; N,N', N" tris 2:2 dimethylethylenetrimesnmide, etc. The N,-N',N"-trls alkentrimesamides and their preparation are described in U.S..Serial No. 823,152, filed August 7, 1959). Q may also be may contain atoms otber'than carbon, e.g. oxygen, tillstirrer, thermometer, condenser and dropping funnel. To the flask was added a solution of 41.5 g. (0.3 M) of potassium carbonate in 50 ml. of water, followed by 9.0 g. (0.21 M) of ethylenimine. This mixture was stirred and cooled to 10 C. A solution composed of 27.5 g. (0.1 M)

of triethylene glycol bis chlorocarbonate in 100 ml. of benzene was then added dropwise to the flask with stirring and cooling over a period of about 18 minutes. The

mixture was kept at 10-12 C. during the addition andwas allowed to warm to room temperature after the addiuct (which was tlen had been completed. Stirring was continued for an additional hour. The benzene layer was recovered, dried r over molecular sieve, filtered and evaporated to constant weight under vacuum. 28 g. of n water-white liquid prodidentiiied as N,N-bis-1,2-ethylene (triethylene glycol) carbamate) were obtained, corresponding to a 99% yield thereof. The refractive index.(n of this product was 1.4748 and its density (11 was 1.198. Upon analysis, this product was found to'contain 9.74% of nitrogen and 0.1% chlorine as compared to calculated values of 9.73% and 0.0% respectively. It was also soluble in a 1:1 weight ratio with water, methanol, isopropanol, methyl ethyl ketone, ethyl cellosolve, butyl acetate and toluene.

1) Illustrative of the bis-carbamates which are useful as curing agents in the present invention are:

I N,N-bis-l,2-cthylene (1,4-butanediol) carbamate; N,N-bis-l,2-propylene (l,4-butanediol) carbamatc; N,N'-bis-l,2-butyler\e (1,4-butenediol) carbamate;

N,N'-bis-l,2-ethylene (diethylene glycol) carbamate; N.N'-bis-l,2-butylene (diethylcne glycol) carbamate;

N,N'-bis-1,2-ethylene (triethylene glycol)carbamate; N,N'-bis1,2-propylene (tricthylcneglycol) carbamate; N,N'-bis-l,2 butylene (triethylene glycol) carbamate; N,N'-bis-l,2-ethylene (polyethylene glycol-200) carbamate;

N,N'-bis-l,2ethylene (polyethylene glycol'400) carbamate;

N,N-bis-l,2-ethylene (polyethylene glycol-1000) carbamate; N,N'-bis-l,2-propylcne (polyethylene glycol-1000) carba- The preferred aromatic carbamates are represented by the above formula wherein R is 1,3-phenylene, l,4phenylene, l,l'-isopropylidene-bis-phcnylene, or l,l'-isopropylideno bis (p-phenyleneoxy) di-Z-propanol. The preferred aliphatic carbamates are represented by the above formula wherein R is a branched or straight chain alkylene radical having from about 4 to about 40, preferably from about 4 to about 20, carbon atoms.

Bis-1,2-alkylenamides and their preparation are described in US. Serial No. 832,152 (filed August 7,1959), Serial No. 840,255 (tiled September 16, 1959) and Serial No. 850,330 (filed November 2, 1959). Generally, their preparation involves the reaction of an alkylenimine in an aqueous phase with a solution of a dicarboxylic acid halide in a water immiscible organic solvent in the presence of an acid acceptor at a temperature between about -5 C. and 30 C. illustrative of the N,N'-bls-l,2- alkylenamides in accordance with this invention are N,N'-bls-l ,Z-ethylenadipamidc; N,N'-bls-ethylenpcntadecyladipamide; N,N'-bls-l ,2-butylenadlpamldc; N,N'-bls'1,Z-ethylencplmelamlde; N,N'-bls-ethylene thlodipropionamlde; N,N'-bis-ethylene oxydipropionamide; N,'N'-bll-l ,2'ethylenisosebacamide; N,N'-bls-l,Z-butylenisosebacamide; N,N'-bls-1,Z-butylenisosebacamlde; N,N'-bis-l,2-ethylensebacamide; N,N'-bis-1,Z-ethylensuberamlde;

N,N' bis -l ,2-propylensub eramide;

N,N'-bis-1,2-butylensuberamide;

N,N'-bis-1 ,2-ethylenazelaamide;

N,N-bis-l,Z-propylenazelaamide;

N,N'-bis'.;1,Z-butylenazelaamide;

N,N'-bis-l,Z-ethylendodecanoyldicarboxylic acid amide;

N,N'-bis-1,2-ethylentetradecanoyldicarboxylic acid amide;

N,N'-bis-l,2-propylentetradceanoyldicarboxylic acid amide;

N,N'-bis-1,2-ethylenhexadecanoyldicarboxylie acid amide;

N,N'-bls-l,Z-ethylenoctadecanoyldicarboxylic acid amide;

N,N'-bls-l,2-propylenoctadecanoyldicarboxylic acid amide; N,N'-bis-1,2-propylendodecanoyldicarboxylic acid amide; N,N'-bis-1,2-pentylensebacamide; N,N'-bis-1,2-ethylene monadecanediamide; N,N'-bis-l,2-ethylene-1,4-naphthalenedicarboxamide; N,N'-bis-1,2-propylene-l,4-naphthalenedicarboxamide; N,N'-bis-l,2-cthylene-4,4'-bisphenyl dicarboxamide; N,N'-bis-1,2-propylene-4,4-biphenyl dicarboxamide; N,N'-bis-l,2-ethylene hexahydroterephthalamide; para-(N-l,2-ethylene carboxamidophenyl)-N-1,2-ethylcne acetamidc; N,N'-bis-l,2-ethylene isophthalamide; N,N'-bis-l ,l-dimcthylethylene isophthalamide; N,N-bis-l,2-butylene isophthalamide; N,N'-bis-1,2-octylenisophthalamidc; N,N'-bisl,2-ethylcne ltexahydroisophthalamide; etc.

The preferred aliphatic bis-1,2-alkylenamides are representcd by the above formula wherein R is a branched or straight chain alkylenc radical having from about 4 to about 40, preferably from about 4 to about 20, carbon atoms. The preferred aromatic bis-1,2-alkylenamides are represented by the above formula wherein R is 1,3-phcnylcne, 1,4-phenylcne, 1,4-napthalene, or 4,4'-bisphenyl. The following Example B illustrates the preparation.

EXAMPLE B -N,N'-bis-ethylene isosebacamide is prepared by the reaction of ethyleneimine with isosebacoyl dichloride to produce the desired substantially pure monomer, with hydrogen chloride as a by-product. Specifically, it may be prepared as follows: A solution of about 95.6 parts of isosebacoyl dichloride prepared from isosebacic acid dissolved in 400 parts of diethyl ether is added dropwise with cooling and vigorous stirring to a flask containing a solution of parts of potassium carbonate and 43 parts of ethylenimine in 800 parts of water. The temperature of the mixture is maintained below 15' C. and the acid chloride is added at a rate of approximately 1 part per minute. i The reaction mixture is allowed to warm gradually to room temperature, while stirring, for an additional hour. During the total reaction period, the pH of the reaction mixture has dropped from approximately 12.5 at the beginning of the reaction to about 8.6 at the end. The ether layer is separated, dried over solid anhydrous sodium hydroxide at 0 C. for 1 hour, the sodium hydroxide is removed by filtration and the ether removed from the filtrate under reduced pressure. The resulting reaction product, N,N'-bis-l,2ethylenisosebacamide, remains as a water-white liquid.

The mechanism by which reaction between the polyalkylene polysultide prepolymers and the polyfunctional alkylenimine derivatives react is not fully understood. A possible mechanism for this reaction may be illustrated as follows:

wherein Q, R, R", R'", n and z are as previously defined. Regardless of the validity of this theory, which does not in any way limit the scope of the invention, these two constituents do react to form addition polymers.

The poiyalkylene polysulfide prepolymers and the polyfunctional alltyleneimine derivative are both capable of homopolymerization in the presence of suitable curing agents to solid resinous or elastomeric compositions. In the case of the polyalltylene polysulfide prepolymers these curing agents may be polyfunctional amines, sodium, potassium and ammonium chromates and bichromates, etc. In the case of the polyfunctional alkylenimine derivatives, weak or strong acids and bases act as curing agents. Among the acids are the heavy metal chlorides, such as zinc or lead chlorides, the mineral acids, such as hydrochloric, sulfuric or phosphoric acids, sulfonic acids, such as p-toluenesulfonic acid, and other acids. Another catalyst which is eii'ective is the boron-triiluoride molecular addition product with monocthylamine. Among the bases are sodium methoxide and amines such as ethylene diamine or monocthanoiamine. In the presence of a suitable curing agent, substantially all proportions of the polyalkylene polysultide prepolymers and the polyfunctional alkylenimine derivatives may be copolymerized. In mixtures containing a great preponderance of one or the other constituent, therefore, it is possible to achieve simultaneously polymerization among units of the major constituent itself and between units of the major and minor constituents. The final cured polymer molecules will thus include the residues of units of both constituents in the relative amounts in which they were originally added. It should be noted that by adding only an extremely small amount of the minor constituent it is possible to approach the composition, and hence the properties, of the homopoiymer of the major constituent as closely as is desired. Therefore, in order to realize the novel properties of the copolymers of the present invention it is necessary to add at least a significant amount of the minor constituent. An amount of about 5% or more yields a signficant change in properties.

if desired, fillers can be added to the composition before curing, as well as dyes or other substances which may be considered as adjuvants and the like; for example, accelerators, antioxidants, and catalysts. The finer tillers are good reinforcing agents for these systems, neutral tillers such as calcium carbonate, iron oxide and titanium dioxide being preferred. Acidic fillers such as certain carbon blacks and silicas can also be used under certain circumstances. The rubbery copolymers of the invention can generally be compounded with any of the usual compounding agents, as well as with the usual antioxidants, accelerators, deodorizing agents, reinforcing agents, softeners, etc. The addition of and increase in amounts of tillers, pigments and reinforcing agents will in general increase the hardness, toughness and tensile strength of the elastomeric polymers.

The sdhesiveness of compositions of the invention which are cured in contact with metals, glass, resin-coated objects, etc. may be increased without destruction of other properties by the addition of various resinous or plastic compositions. These other polymers are generaliy added in the ratio of from about i to about 18 to 20 parts per I00 parts of the copolymer of the present invention although as high as 30 or even 50 parts can be used. When used in the lower range of proportions the cured compounds tend to be resilient and even slightly softer than the copolymers; when used at a ratio of 30 parts or more, the cured compounds may be harder and more brittle. Primarilydue to their outstanding propertiesof resistance to heat, water and to chemicals, the phenolic and epoxy resins are preferred for this purpose for use 'with the compositions of the invention. In this regard, the term "phenolic resins" is intended to include the resinous products obtainedfrom the condensation of almost any phenolic body with an aldehyde such as fornialdehyde or furfural. Likewise by epoxy resins" IS meant any epoxy reaction product for example the product obtained by reacting a poiyhydroxy compound and epichlorohydrin. The cured composition resulting front the conjoint use of fillers, pigments, modifiers and resin-. ous components with the copolymers of thefinventton may contain as low as 40% by weight of such copolymers. Other resinous or plastic compositions which may be added to the copolymersof the invention are alkyd resins, soluble vinyl polymers and copolymers, chlorinated rubbers, cellulose esters, cellulose ethcrs, acrylic acid ester polymers, vinylidine polymers and copolymers, rubber hydrochloride, chlorinated diphenyls, urea formaldehyde polymers, toluencsulfonamide-formaidehyde rcac tion products, coumarone-indene polymers, styrene polymers and copolymers, etc.

In the preparation of the cured compositions of the invention, both the polyalkylene polysuifide prcpolymers and the polyfunctional alkylenimine derivatives may be employed in either liquid or solid form, which are mixed to produce curable compositions. Thus mixing can ordinarily be easily accomplished either when both constituents are liquid or when the poiyalkylene polysulfide prepolymer is liquid and the polyfunctional alkyienimine derivative is a solid. Likewise the mixing can be relatively easily accomplished when the polyalkylcnc polysuliide prepolymer is a solid and the polyfunctional alltylenimine derivative is a liquid although the use of a rubber mill may be necessary. In cases in which both constituents are solids no particular mixing diflicultics are usually encountered although the use of rubber milling equipment is almost always necessary. Other aids to mixing are solvents which may be removed as by evaporation upon completion of the mixing and the application of a moderate degree of heat to lower the viscosity of the'liquid constituents and to iiquit'y solid constituents.

The liquid compositions of the present invention are particularly well suited for use as sealants because the polymers produced therefrom have good resistance to chemicals, solvents and aromatic oils, as well as a high degree of dimensional stability on curing, ease of compounding and easily controlled curing rate. To improve their characteristics as sealants they may be compounded, if desired, with pigments, fillers, resinforcing agents, antioxidants, accelerators, deodorizing agents, softeners, etc. These uncured systems with curing agent added may be introduced into joints or spaces which are to be sealed, using the ordinary means available to the art, such as caulking guns and the like. The compositions undergo i spontaneous curing, producing solid products which provide effective sealing means. Alternatively it will be ob- (I vious that metal sheets or the like which are to be sealed f can be coated with the liquid compositions along the lines of juncture, for example, on the abutting portions of lap joints, and then riveted, crimped together or otherwise joined, whereupon the elastomer produced on curing will seal the joints. Likewise, by employing materials 1 of low viscosity or by employing solvents to reduce viscoslty, the composition in which curing has been initiated can be utilized to coat surfaces, for example, interior surfaces of fuel tanks and the like, to seal the joints thereof and at the same time provide a substantially fuel-proof lining theretor.

in order more clearly to'dlsclose the, nature of the present invention, a number of specific products and compositions in accordance with the invention will"'now be described.

It should be understood, however, that this is done solely by way, of illustration and is intended neither to delineate the scope of the invention nor to limit the ambit of the appended claims. Lots Example 1 M u 1 Several rubbery materialsare prepared for the purpose of comparing the properties of unfilled copolymers of a M1m|npmpcmc,;i polyalkylene polysulfide prepolymer and the bis-amides sim g t with a conventional homopolymer of the same poiy- To minim 55i: 3Q 0 2A alkylene polysulfide prepolymer. The polyailtylene polyl l hi 1 t ulfide prepolymer used in these mixtures is a thiol-terfi ipi feig ni iii'g ufii n g l l il t x 'minated liquid polymer of his (ethylene oxy)methane w l l i t 10.10 1. 02 having a viscosity at 25' C. of 350-450 poises, a number llgl it lga l fi l lt l r h i moon H5 H5 average molecular weight of 4,000 and a pour point of "f A 40-40 40-40 35 P. (which is available from the Thioltol Corporation m of Trenton. NJ., under the designation "Thioltol" liquid Thu mt pmmm or (A80) m Sm Tho mm P y LP-2)' ltiiluro is designated M either adhesive (A) or cohesive (O).

Th copolymcrs are prcparcd b i i h l dk might: test value 2 is the lowest figure measurable en the equipment ene polysulfide prepolymer and the bis-amide before addln;i\'i(lllil0ll3l( ):4lf nilheres at; strong}? to irtliil'nlnullll alter "{li'lliffl, l O O 0 nwu (1' Di mg 'f ammomchyl) The at 1 26' F. that it lni ls co izgfv iy ior gitls pullei l away from tho homopolymer is prepared by mixing the catalyst (lead '20 aluminum. phumlmc) Md Lots la, lb, 10, and id are useful for sealing the seams crater (stearic acid) before adding the polyaikylcne polyof tanks. sulfide prcpolym? composluom and cure of the Three additional rubbers are prepared utilizing the nous are m the followmg process of mixing of similar lots in the series la through 1: except that a solvent is added: Lots Lots la 10 1e id ll 1 la in "iiiii "i lii'i 1 '0 ya 3 one xlll (o prrpo yc m a:

5 2 .Tfif..iLfffiiflfli' 100 100 m0 100 l00 li lg g gmm r f fifi id 9'0 9 o g? ihlokol liquid polymer yen sop in am e... n as:.iziiiiaiaaaiiiiiiz;1 p n 1.1 1-1 1.1 1.1 Lend dioxide. as M (flame 2 Dlbutylphthalnte 0.7 Mm 5 if Xylol 10.00 14.0 7.45 Ambient temperatures only (Le. x x n! bbc b d db I d I. ese ru rs are su ecte to 0 won an wei t oss F x X x tests as follows:

I Available from the Rohm and lliuu Co. of Philadelphia, Pennsyi- I u vanls under the designation D.\tI'-30.

lip on: Lots in and I: are straw-colored and translucent, lots lb and iii are red and translucent and lot is is reddlslvbrown and opaque. U A

The results of the tests performed on these rubbers are to Mummunr, as follows: 0 mini 2.0 2.2 0.4

Alter tti hours immersion in 70:30

isooetnneztoluene 2. 0 2. 0 O. 3 Lots Percent adhesion loss in tuel l3. 5 0. l 20 Weight ions: ieroint wright los nltrr fliinys' immersion in Type 3 FUEL... 15.0 2l.l la lb 1: id is 00 I The test procedures at MIL 7502A are used. Tensile w The properties of the copolymers of the invention are i st 00 is st 7:! gigfi zgg fl mg 98 03 oiten improved by the addition of other resins and fillers.

t mnt man: about [H (TM 66 This is illustrated by lot ll.

Composition: Let i] Low temperature ti rtbititx: Polyalkylene polysuiiide prepolymer (ThioltoP' "30 53 liquid polymer-LP-2) so Boott ilrittloness, r. 'N,N -bis-ethylenisosebacamide (ABTM o wet-m) Lead dioxide 7 5 to to to to to 00 4s. s0. -38. t3. b0. .Dibutyl phthalate 6.8 "2 5%,, "3 m .l'fifi": Stearie acid 1.7 rnmersed hr. at in Carbon black filler 30 v'im' i' n n n Lot 1] is prepared by mixi the polyalkyle i lfid n8 ne po ysu e m f ig m 0 prepolymer, the bis-amide and the carbon black and then m r 45 a m 23 M adding the lead dioxide, the dibutyl phthalate and the stearic acid which have been mixed separately. It is a viscous mixture which is cured for hours at F I 'I nail rtl s tests are run on dumbbell s tmsns (0.0" between bonel: miii if 10$ mgaration rate OIWIminute Z TMt values correlate At the end of this cure a solid having a Shore A-2 hard- Wllh 51 ABT D 70 ness of 35-40 is obtained.

00% -Velume swelling, percent, wherein D isthe density Ex m I 2 oi the ssmple izo e rslini nersgi 3| is t ha da i ty 0i th e hiel de. a p e I! I l 00. 0 W0 [I O 0 l8! 6 I 0 en 0 glte t im oiimmerston betoi'e removal clan retained uelnndOls the A pfflysulfido prcpolyfncr whch a weight of the sample alter immersion and a or removal 0! any retain d thiol-terminated liquid polymer Of bis(ethylene oxy) mi. 75 methane having a viscosity of 25' C. of 7-12 poises, a

1 1 1 2 number average molecular weight of 1.000 and a pour The utility-of lots 24:, 2b, 2c and 2d includes the sealpoint of -15 F. (which is available from the Thioltol ing of the seams of metal tanks. Corporation of Trenton, NJ., under the designation Lots 2g and 211 are examples of filled copolymers of "'Ihioltol liquid polymer LP-3) has been used in this the invention. They are prepared by mixing the polyexample. Lots 2a through 2: are prepared by the meth- 5 alkylcne polysulfide prepolymer and the bis-amide and ods of lots 1:: through it and lot 21' is prepared by adding adding the filler and the other ingredients.

the p-quinondioxime and the diphenyl guanidine to the polyalkylene polysulfide prepolymer. Of the two controls, lot 2: will cure at room temperature or with only a moderate heat cure while lot 2} requires an extended heat cure.

. Com sltlona:

2b a 2d a 2, i di ynlkylone polysultldo prepolymer ("Thickol' 'ltqultl polymer LP-(t). 50 50 com mom: N, h 'bts-othylnntsosetmeamtde 50 b0 l Tyelkyhne l um Titanium riloxido tiller 60 w w Wight" rfiahat'rsme t a t l? fl zdgfzg' M m Builur (powdered) .1

eeheeemlde 34.! 34.3 N N ht: ethytentmph- 2 qiiili 'iimai in; m m

me I nonle I e renal: u 1.: 1.: 1.: The resulting mixtures are mobile liquids WhICh cure {,ga af gmmg in hours at 160' F. to solids having the following 0 mt properties: A; lloxime- )tphenytguenldtm He He tum l I! 81 m on (mm-n i X x I u cumummteo- Ethoun). 2; 2% m 24 Ap armor: Late 20, 2e and 24 no straw-colored and 24 2h tramu neent. lot 2b In red and treatment, lot 20 ll reddllh- 80 brown opaque and lot 2! in black and opaque.

Ten l t le Properties: 3 m of Performed on mbbm m i fi hih fileli 'kgtiij "3:: 82 .5 0w}: 0 l roe reen 0 0 u 0 Volume swelling FXBTM D 471-401 B 70:30 tsooetene=tolucne (48 hr. at 180' 1-1), 0 0 percent w atler (706m at 180' 12.),8 pr -reont... 76 0 0 2 b a u 2 a mom on, pcroen u "net-god at 0- 2.42 1.73 4.2x 3.7x Tensile Pr perties: 7 4.55 4.15 Tensile strength. p.11. MI 83 108 88 It! 70.90 704,0 menu ten percent; 100 m m to: m 240 an a hmh. at. o o o o o o llardncsl: share 4...... n to ze t; so to 32: 0 26st: 20 to Inbv rmtempereture flesh i Oeiimm T... r..... -u.t +21! -4e -2e -se -4s Exampl 3 Boottbritlkneu, TI, -z7 -u -'.'a -a0 -tt 45 F- W In this example a polyalkylcne polysulfldc prcpolymcr 40. -44. -z2. -aa. a0. -43.

Volume millnlinnter which is a thiol-termmated liquid polymer of bls(ethylcne (ABTM D 471491 oxy) methane having a viscosity at 25 C. of 350-450 lmmcned 70 hr. at m 1*..prrwnt n: no 1a.: m m 1.4 9 m. a number uvcraac molecular weight of 00 Volume 3 "a and a pour point of 45 F. (which is available from the gzeteutet'eu mum Thiokol Corporation 0! Trenton, N.J., under the desig- E" nation "l'hloltol" liquid polymer LP-32) is reacted with in exam le lmmtlfiddfiqlhflllr r.. two bis-amides to form rubbery solids. W-------------- n a a The following lots are prepared by the methods of 6t! lots la through 1c. in a a: a 2 I Lou 4A 2A 2A 00 MA 2A 2A a sh 3c a4 a 00 2A 2A Com tttone: l'lboledptooaiumolhflirm Mlmmueed. Thetype 0! PT I htlun a am o-a me either 1mm Al or eohutvi (0). i -i' f mm,

on Lv-n) 100 100 100 100 100 N,N'-btn-ethyientaoeebnmmtde.... 8.0 8.0 L N,N"bk-ethrlenteophthnlnmtdo.. 7.4 7.4

'irttdtmethy nmtnomethyl) phenot ..11 1.111 It 2| )4 Lend dioxide 7.5 Dtbutytphthulete. 0.7 Btearieeeid. .8

Reflnteneetoeet at hleh terggereture cum wyh tenmere ure ulnl hr. at Ambient temperetum only (Le.

[.tn 70-76 F.)....... X X Ye ht loeagtg tn gyettnnpemnt. 7.9! 6.78 zlihnettoo 22.... X X X 401045 8M0 to 40mm 401 4 4 45 35 Appearance: Lot: 8e, 3e and M are Itmw-onlomd and trnnalueont, lot

86 ll red and trnmlueent and lot :u is reddish-brown and opaque.

13 The results of the tests performed on these rubbers are as follows:

Lots

30 8b 3c 3d 8| Tensile properties:

Tensile strength, 1) s.i as 71 9t 91 at Bieuntion peroon 187 110 128 143 Bet st-bmir, o o a o o Hardness: Shore 4 25 to 88 to as to 33 to 83 80 43 40 88 Low temperature flexibility:

Gehmsn T, -ss -42 -44 -43 -55 Scott brittleness, Ts, F"... 40 -42 -38 40 -t to-M lo-M to-il to-ii to-i8 Volumessrellin insrater(ASTM D (ll-491 Immersed 70 hr. at ill I., percent (9.3 27.0 22.8 31.3 7.4 olume swelliuma 70:30 isooetane:teluene i (Calculated according to the inrmula set out in Example i):l mrnsrsed ss hr. at m percent I 24 23 23 iii Adhesion properties: i

To stars 4A 120 2A To aluminum 7C 0C 2A To stainless steel d0 lIiO 2A 'The test procedures oi Mib-B-Btm A80) are used. The t of failure is designated as either adhesive (A or cohesive (C). We

in addition, lot is adheres so strongly to aluminum that it fails co- Lot 3] is another example of a filled copolymer of the invention. it is prepared by the method of lot lm the sulfur being mixed with the lead dioxide, dibutyl phthalate and stearic acid before mixing them with the other ingredients.

Composition: Lot 3] Polysiltylene. poiysulnde prepolymer ("'Ihiokoi" liquid polymer LP-SZ) 50 N,N'-bis-ethylenisosebaeamide 50 Lead dioxide 6.6 Dibutylphthalate 5.9 Stearie acid 1.6 Sulfur .1 Carbon black tiller 30 it is a viscous mixture which is cured for 90 hours at 160' P. At the end of this cure a solid having a Shore A-2 hardness of 35-40 has formed.

Example 4 In this example a polyalkylene poiysuiiide prepolymer has been used which is a thiol-terminated liquid polymer of bis(ethylene oxy)methane having s viscosity at 25' C. of iii-15.5 poises, a number average molecular weight of 1.000 and a pour point of 5 to P. (which is avallabie from the Thiokol Corporation of Trenton. NJ.. under the designation "Ihioltol" liquid polymer Li -33).

The following lots are prepared by the methods of lots 24, 2e and 2] respectively.

Lots

to 4b 4e Compositions:

lolyalkylane faolysulfide propolymer hioiroi" liquid polymer 41 -33) 100 I09 N,N '-bis-ethylenisosobacamida 36. 3 Trl(dimathyl antluorncthyl) cnol 1.4 Load dioxide Dlbutylphthala Btanrlo acid g-Quinondloxime 7 l honyiguuuidine 3 Cure: lours at 100 F 2M 2% 2i Appearance: Lot 4a is red and translucent, lot 4b is reddish-brown and apaque and lot 40 ts black and opaque. The results of the tests performed on these resins are as follows:

Lots

in 4b 4c Tcnsiln promrtimt:

'icnsllu strength, p.s.i i2! 70 I32 Elongation, pereunL. am Sill) Set at break, pormut 0 0 (i Hardness: Show A-2 33 to 38 20 to 25 23 to 28 Low temperature litxibill Oohmnn F -i7 -M li2 Scott brittleness, 'la, P... i3 to --47 iii to M i0 to -43 Volume swcllinr in wutcr (ASTM D i7i-49'l i"): Immersed 70 hr. at l80' F.. pcrccnt 22.8 7. 4 22.8 Volume swelling in 7tiz30 Lsooo tnnanoluane uei (Calculated accord to the formula set out in hxnmple i): immersed 48 hr. at 180' percent i8 33 23 Resistance to axing at high tear perature (High temperature aging 70 hr. at 2.50 i. in air):

Weight loss during aging,

D m 0.12 8.85 Hardness. Bhoro A-I:

lit-fore a ing 40-45 85-40 After ng n; 40-45 5-10 Lot M is another example of a filled copolymer of the invention. it is prepared by the method of lot 2):.

The resulting mixture is a mobile liquid which cures in 20 hours at F. to a solid having the following properties:

Tensile properties: Lot 4d Tensile strength, p.s.i. 280 Elongation. percent 20 Set at break, percent 0 Volume swelling (ASTM D 47i-49T "8"):

70:30 isooctane:tolucne (48 hr. at F.), percent Water (70 hr. at 180' R), percent 7.4 Water absorption (submerged at 70-75 F.):

1 day 2.42 7 days 5.35 it days 6.9 Hardness: Shore A-Z 70-90 Example 3 Five fast curing casting resins are prepared from a bisamide, a liquid epoxy resin which is a reaction product of epichlorohydrin and 2,2-bis (4-hydroxyphenyl)-propane having a Brookfield viscosity of 110170 poises and an epoxide equivalent weight of 180-205 (which is available from the Bakelite Division of the Union Carbide and Carbon Corporation of New York 17, New York, under the designation ERL-2774), a polyalkylene polysulfide C. At the end of this time a soft, tacky, thixotropic maprepolymer (which is available from the Thiokol Corterial is formed.

P ation of Trenton, NJ., under the designation Thio- Both of these materials are useful as sealers for pipe kol" liquid polymer LP-3), resorcinol and tri(dimethyl threads, particularly for use in lines which are carrying aminomethyl)phenol. The resins are prepared by mix liquid hydrocarbon fucisy am also as ing parts A (a mixture of the his-amid th cpoxyjgsin 1o placeable channel (or injection) sealers in aircraft, par and the resoreinol and B (a mixture of the polyalkylene liwlarly f Scaling hydrocarbon fuel Siofflgc p wn It polysulfide polymer and the catalyst). The resulting li is usually possible to improve the properties of these mauids cure to solid resins at ambient te eratur s, By terials for use as sealers by techniques of compounding, p e a ng the liquid resins, the curing rate may be aesuch as the addition of fillers, well known to those skilled celerated so that tacit-free solids are formed more quickly. in the art.

'l'he compositions and cures of the various lots are Examp 7 gwcn m the followmg table: About 33.2 parts of N,N'-bis propylenisophthalamide are mixed into 100 parts of "Thiokol" liquid polymer LP-S followed by 1.3 parts of tri(dimethyl aminomethyl) phenol catalyst. The mixture is cured for 24 hours at 54 120' C. At the end of the cure, a soft, tack-free solid has formed. flm fifi in another lot 9.3 parts of N,N'-bis propylenisophthal- N,N"ilil-(ul)'kfll.1)- amide, 100 parts of Thiokol liquid polymer LP-Z and 'glm flgg g 25 1.1 parts of tri(dimethyl aminomethyl) phenol are mixed Iseem 12.40 14.05 tars by the same method and cured 24 hours at 120' C. At

mm the end of the cure, a soft, tack-free solid has formed. hix'lffifillliff. v.40 412s 47.2s 41.20 n70 Exam 8 rm nl Mo About 100 parts (by weight) of "Thiokol" liquid polyflmg P: mer LP-2, and 10.7 parts of N,N'-bis ethylendodeeanoylmer hh it oi dicarboxylic acid amide are mixed thoroughly and l.l

no am no Mo a" parts of tri(dimethyl aminomethyi)phenol are subsefl(dlmethfl lmquently stirred in to yield a homogeneous mixture. A cum 'xm'gg tough rubber is formed within 24 hours at room temperaut-tumnmmum)" 2e 1 to 20 is lure. lntttal temperstun 0! mixture C.) 28 56 85 28 25 Examplg 9 The preparations of five lots illustrating the composimf of performed on as tlons of the invention which contain relatively large amounts of bis-amides are given below. These lots are prepared by mixing the bis-amide (which in lots 9a, 9b and 90 has been heated until it is liquified) with the polyalityiene polysulflde prcpolymer and then adding the cat- 6 0 k d l alyap gi 'iu'b h 40s 2.000 2 1 2.700 1.200

I 18.2 00 we 10s 1.0 M W simmenstle at. x

(m 00.0 01.0 a 33, Md m m m nensfildlmethylsmlne l t 1 c m I "M Trt( methyl lmlnomothyl) 1 (WM) M Curenoiiii'i'iihb'r st m s t as; in; gains mph (pal. x M m lmpeet strength (It. lbJtneh ggzgw mrtw m w w M at: stat-at.salts-alarmist:stares? tg fi 3 40 2s 00 as as u Mimi Dm' ri s.t 1.0 1.00 2.32 0.00 05 AITM D 096-. 0d 00 Example 6 Tensile properties:

About 33.2 parts of N,N'-bis prepylenterephthal- E -v- & 38

amide are melted and mixed into parts of Thlokol onmon'wmm liquid polymer LP-3 followed by 1.3 parts at tri(dimethyl aminomethyi) phenol catalyst. The mixture is heated for 24 hours at C. and a soft, tacky, thixotropie material is formed.

16 In another lot, 9.3 parts of N,N'-bis propyienterephthalamide, l00 parts of Thioltol liquid polymer LP-Z and 1.1 parts of tri(dimethyl aminomethyl) phenol are mixed by the same method and heated 24 hours at 120 Example 10 mer which is a liquid polymer of bis(butyiene oxy) methane (available from the Thioltol Corporation of Trenton, New Jersey, under the designation "Tltiokol" liquid polymer ZL-205) and 6.6 parts of tri (dimethyl aminomethyl) phenol are added subsequently. This mixture gels after 4 hours at room temperature. Test results obtained from samples cured at room temperature are as follows.

, Tensile properties:

Tensile strength, p.si. 135 Elongation, percent 75 Set at break percent Tensile strength run at 400' F. after minutes aging at 400' F., p.s.i. 150 Elongation at 400' F., percent 65 Hardness:

Shore A-2 50 Low temperature Flexibility:

Gehman T F. +203 Volume swelling (AST M 471-49T "8"):

70:30 isooctane: toluene (48 hr. at

180 F.) 15.1 Water (70 hr. at 180 F.) 15.1 Water absorption, percent (submerged at 1 day 21.4 7 days 23.8 ll days 22.6

Example II 11.1 parts of N,N'-bis-butylenisosebacamido are mixed with 100 parts of "Thiokol" liquid polymer LP-2 to form a homogeneous pourable mixture. 6.67 parts of p-quinone dioxime, 0.5 part of diphenyl guanidine, and 0.2 part of sulfur are added and the mixture is cured at 160' F. for 3% hours to produce a soil, rubbery solid.

Similarly, 9 parts of N,N'-bis-ethylenhexahydroisophthalamide (a white solid which may be prepared from hexahydroisophthaloyl chloride and cthylenimine by the process herein described for the preparation of bis-amides) are mixed with 100 parts of "Thiokol" liquid polymer LP-2 and 1.1 parts of tri(dimethyl aminomethyl)phcnol catalyst are added subsequently. This mixture cures after 16 hours at room temperature into a clear, light green colored, soit, non-tacky rubbery material.

Example )2 10 parts of N,N'-bis-cthylenisosebscamide, 100 parts of Thiokol ST (a thiol-terminatcd crosslinkable polysulllde crude rubber which has a sulfur rank of 2.25), 60 parts oi carbon black flllcr and 0.5 part of stearic acid are milled together on a rubber mill for about 2 hours without heating the rolls. A black crepe-like sheet is produced. On curing for 30 minutes at 287 F., a soft rubber is obtained which is suitable for oil resistant gasket applications.

Example 13 6.55 parts of N,N-dibutyl-N'N-diethylene phosphoric triamide, 5.0 parts of 'lhioltol" liquid polymer LP-3 and 1.0 part of tri(dimethyl aminomethyl)phenol catalyst are mixed together thoroughly. The mixture is allowed to remain at room temperature for 24 hours and is then given a heat cure of 2 hours at 160' F. and 24 hours-at 212' F. At the end of this time the mixture has cured to a dark brown opaque rubbery material. This copolymer may be used as a protective coating for various substrates such as wood, metal, etc. as well as for a sealant.

Example 14 About 5.8 parts of hexyl-N,N'-dlethylene phosphorodiamidate, 5.0 parts of "Thlokol" liquid polymer LP-3 and 1.0 part of tri(dlmethyl amlnomethyl)pbenol catalyst are mixed thoroughly to form a reddish brown compatible solution. This solution is allowed to stand for 24 18 hours at room temperature and is heat cured for 2 hours at F. to produce a soft, cherry red rubber-like material. The liquid solution may be coated onto various substrates, such as wood or metal and then cured in place to form a protective coating. It may also be used as a sealant.

Example 15 About 5.1 parts of butyl-N,N'-diethylene phosphorodiamidate, 5.0 parts of "Thiokol" liquid polymer LP-3 and 1.0 part of tri(dimethyl aminomethyl) phenol eatalyst are mixed thoroughly to form a reddish brown solution. This solution is allowed to stand for 24 hours at room temperature and is then cured for 2 hours at 160 F. The resulting solid is a slightly tacky, tough, rubbery material suitable for use as a sealant.

Example 16 About 6.2 parts of butyl-N,N'-di-2-methylethylene phosphorodiamidate, 5.0 parts of "Thiokol liquid polymer LP-3 and 1.0 part of tri(dimethyl aminomethyl)- phenol catalyst are mixed thoroughly to produce a reddish brown solution. This solution is allowed to stand for approximately l6 hours at room temperature and is then heat cured for 2 hours at 160 F. and 24 hours at 212' F. At the end of the cure cycle, a soft, transparent, cherry red, tacky rubber-like material has been formed which may be used as a sealant -for wood, metals, etc.

Example 17 About 7.2 parts of p-chlorophcnyl-N,N'-di-2-methylethylene phosphoric diamide, 5.0 parts of "Thiokol" liquid polymer LP3 and 1.0 part of tri(dimethyl aminomethyl) phenol catalyst are mixed thoroughly to form a reddish brown liquid solution. This solution is allowed to stand for 24 hours at room temperature and is then cured for 2 hours at 160' F. to form a slightly tacky, amber colored, flexible rubbery composition suitable for use as a sealant.

Example 18 Example I 9 3.32 parts of N,N'-bis-2-methylethylcne-l,3 benzene disulfonamide, 10.0 parts of "Thiokol" liquid polymer LP-3 and 0.42 part of tri(dimethyi aminomethyl) phenol catalyst are mixed thoroughly at room temperature to form a liquid which exhibits a significant amount ot' exotherm. Within 5 minutes alter mixing the liquid is cured to a tack free, tough, brown rubbery material which forms a useful coating or sealant when cured in place.

Example 20 8.45 parts of N,N'-bis-l,2-ethylene[1.1-isopropylidenebis(p-phenyleneoxy) di-2-propanol1carbnmate, 5.0 parts of "Thiokol" liquid polymer LP-3 and 1.0 part of tri- (dimethyl aminomcthyi) phenol catalyst are mixed thoroughly at room temperature to form a light brown paste-like material which cures within A hour at room temperature to a hard opaque resin-like material. The past may be cured in place to form a protective coating.

Example 21 6.15 parts of N,N',N"-tris-2-ethylethylenetrimcsamide, 5.0 parts of Thlokol" liquid polymer LP-3 and 1.0 part of tri(dimethyl aminome-thyl) phenol catalyst are mixed thoroughly at room temperature to form a clear, pour- 19 able yellow liquid which cures within ten minutes at room temperature to form a clear, tough, solid yellow resin. This material adheres strongly to glass and aluminum when cured in contact with these materials of construction.

Example 22 6.35 parts of hexamethylene N,N'-diethylene-urea, 5.0 parts of Thiokol liquid polymer LP-S and 1.0 part of tri(dimethyi aminomcthyl) phenol catalyst are mixed thoroughly at room temperature to form an opaque, pink colored, viscous paste which is allowed to stand .overnight at room temperature and then heated for two hours at 160 F. to form a hard, rather brittle light brown resin. When the paste is applied to a substrate such as wood and then cured in place. a useful protective coating is formed.

Example 23 6.5 parts of toluylene-N,N'-diethylene urea, 5.0 parts of "Thiokol" liquid polymer LP-3 and 1.0 part of tri- (dimcthyl aminomethyl) phenol catalyst are mixed thoroughly at room temperature to form a viscous, light yellow paste which is heated for two hours at I60 F. to form a hard, opaque. light brown resin. When cured in place on a substrate such as wood a useful protective coating is formed.

The terms and expressions which have been employed are used as terms of description and not of limitation, and it is not intended, in the use of such terms and expressions, to exclude any equivalents of the feature shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.

What is claimed is:

l. A reaction product of a polyalkylene polysultide prepolymer which contains recurring disulfide linkages (-44-) and which is polyfunetional in terms of mescaptan groups and a poiyl'unctional aziridine ring-eontaining compound of the formula:

Clls

where Q is an n-vtticnt radical, n is at least 2. N is linked to an atom having a valence from 4 to 5 and R and R" are selected from the group consisting of hydrogen and an alkyl group, said Q having no active hydrogen atoms.

2. A reaction product according to claim 1 in which Q contains the group 3. A reaction product according to claim 1 in which Q contains the group 4. A reaction product according to claim 1 in which the polyaiitylene polysultide prepolymer is a thlol-tenninated liquid polymer of his(ethylene oxy) methane.

5. A reaction product according to claim 1 in which the polyalkylene polysultide prepolymer is a thiol-termlnated liquid polymer of bis(butylene oxy) methane.

6. A reaction product of a poiyalkylene poiys'ultide prepolymer which contains recurring disuliide linkages (SS-) and which is polyfunctlonai in terms of mercaptan groups and a polyfunctlonal azirane ring-containing alltylenamide which is a derivative of a polycarboxylic acid, the carbonyl residue of each carboxylic group thereof being bonded directly to the nitrogen atom of an azirane ring.

7. A reaction product of a polyaikylene polysultlde prepolymer which contains recurring disulflde linkages (SS) and which is polyfunctional in terms of mercaptan groups and a N,N,N"-tris-1,2-alkylentrimesamide.

prepolymer which contains recurring disulfide linkages" (S-S) and which is polyfunctional in terms of mercaptan groups with N,N'-bis-ethylensebacamide.

ll. A reaction product of a polyalkylene polysulfide prepolymer which contains recurring disulfide linkages (-S-S--) and which is polyfunctional in terms of mercaptan groups with N,N'-bis-propylenterephthalamide.

12. A reaction product of a polyalkylene polysultide prepolymer which contains recurring disulfide linkages (-SS-) and which is polyfunetional in terms of mercapto groups with N,N'-bis-butylenisoscbacamide.

13. A compounded rubber composition comprising in admixture u polyalkylcne polysullide prepolymer which contains recurring disullide linkages (SS) and which is poiyfunctionai in terms of mcrcaptan groups and a compound of the formula:

where Q is an n-vaient radical, n is at least 2. N is linked to an atom having a valence from 4 to S and R and R" are selected from the group consisting of hydrogen and an alkyl group, said Q having no active hydrogen atoms.

15. A surface coated with a cured product of a polyalkylene polysulfide prepolymer which contains recurring disulfide linkages (-SS-) and which is polyfunctional in terms of mercaptan groups and a compound of the formula:

Ciis

where Q is an n-vaient radical, n is at least 2. N is linked to an atom having a valence from 4 to 5 and R and R" 3 are selected from the group consisting of hydrogen and an alkyl group, said Q having no active hydrogen atoms. 1

16. A reaction product of a polyaikyienc poiysulfide prepolymer which contains recurring disuliide linkages (--SS--) and which is polyfunctional in terms of mercaptsn groups and an N,N'-bis-l,2-alkylensulfonamide.

17. A reaction product of a polyalkylene polysulfide prepolymer which contains recurring disullide linkages (S-S-) and which is polyfunctionai in terms of mercaptan groups and a bis-1,2-alkylene earbamate.

18. A reaction product of a polyalitylene polysulfide prepolymer which contains meaning disuliide linkages (-SS) and which is polyfunctionai in terms of mereaptan groups and a bis-1,2-alkylene urea.

19. A reaction product of n polyaikalene polysullitle prepolymer which contains recurring disuliide linkages (SS) and which is polyfunctional in terms of mercaptan groups and a bis-1,2-alkylenamide.

20. A polymeric composition comprising in admixture a polyalkylene poiysulfide: N,N'-bis-l,2-alkylenamide nection product and an epoxy resin, said polyalkylene polysuifide containing recurring disulfide linkages (SS) and being polyfunctional in terms of mercaptan groups References Cited in the file of this patent UNITED STATES PATENTS Carpenter Dec. 13, 1960 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Pa tent No. 3, 119,782 January 28, 1964 Paul Fram It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. I

Column 4, 11nes 29 and 30, for "phosphorodlamlde" read phosphorodiamidate column II in the second table, under the heading "2f" lines 4 and 5, for "20 to 35. read 30 to 35. column 14, in the first table, under the heading "40" line 1 for "109" read 100 column 15, last table, first column, line 2O for "2O read 10' Signed and sealed this 19th day of January 1965.

(SEAL) Alma ERNEST W. SWIDBR' EDWARD J. BRENNER Atte'eting Officer Commissioner of Patents 

1. A REACTION PRODUCT OF A POLYALKYLENE POLYSULFIDE PREPOLYMER WHICH CONTAINS RECURRING DISULFIDE LINKAGES (-S-S-) AND WHICH IS POLYFUNCTIONAL IN TERMS OF MERCAPTAN GROUPS AND A POLYFUNCTIONAL AZIRIDINE RING-CONTAINING COMPOUND OF THE FORMULA: 